Professor Pedro Autreto

@article{GomezQuispe2024,

title = {TPDH-Graphene as a New Anodic Material for Lithium Ion Battery: DFT-Based Investigations},

author = {Juan Gomez Quispe and Bruno Ipaves and Douglas Soares Galvao and Pedro A. S. Autreto},

url = {https://pubs.acs.org/doi/10.1021/acsomega.4c06252},

doi = {10.1021/acsomega.4c06252},

issn = {2470-1343},

year  = {2024},

date = {2024-09-03},

urldate = {2024-09-03},

journal = {ACS Omega},

publisher = {American Chemical Society (ACS)},

abstract = {The potential of tetra-penta-deca-hexagonal graphene (TPDH-gr), a recently proposed 2D carbon allotrope as an anodic material in lithium ion batteries (LIBs), was investigated through density functional theory calculations. The results indicate that Li-atom adsorption is moderate (around 0.70 eV), allowing for easy desorption. Moreover, energy barriers (0.08–0.20 eV), diffusion coefficient (>6 × 10–6 cm2/s), and open circuit voltage (0.29 V) calculations show rapid Li atom diffusion on the TPDH-gr surface, stable intercalation of lithium atoms, and good performance during the charge and discharge cycles of the LIB. These findings, combined with the intrinsic metallic nature of TPDH-gr, indicate that this new 2D carbon allotrope is a promising candidate for use as an anodic LIB material.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{doi:10.1021/acs.langmuir.4c01549,

title = {Ultralow Detection of Mancozeb Using Two-Dimensional Cobalt Telluride (CoTe2)},

author = {Surbhi Slathia and Bruno Ipaves and Caique Campos de Oliveira and Solomon Demiss Negedu and Suman Sarkar and Pedro A. S. Autreto and Chandra Sekhar Tiwary},

url = {https://doi.org/10.1021/acs.langmuir.4c01549},

doi = {10.1021/acs.langmuir.4c01549},

year  = {2024},

date = {2024-07-15},

journal = {Langmuir},

volume = {0},

number = {0},

pages = {null},

abstract = {Pesticides are crucial in modern agriculture because they reduce pests and boost yield, but they also represent major risks to human health and the environment; therefore, it is important to monitor their presence in food. Reliable and precise detection techniques are possible ways to address this issue. In this work, we utilize atomically thin (two-dimensional) cobalt telluride (CoTe2) with a high surface area and charge as a template material to detect mancozeb using spectroscopic and electrochemical techniques. When mancozeb (MNZ) molecules interact with 2D CoTe2, spectroscopic analyses reveal distinctive spectral shifts that clarify the underlying chemical interactions and binding mechanisms. Furthermore, CoTe2’s electroactive sites and their manipulation for improved sensitivity and selectivity toward certain MNZ molecules are investigated by electrochemical studies. The CoTe2/GCE electrode exhibits enhanced electrochemical activity toward the electrooxidation of MNZ. The developed sensing electrode shows a linear range from 0.184 mM to 18.48 μM and a limit of detection of about 0.18 μM. In addition, we employ density functional theory (DFT) first-principles calculations to validate the experimental findings and comprehend the mechanism behind the interaction between CoTe2 and MNZ molecules. The study highlights the effectiveness of 2D CoTe2 as a dual-mode sensing platform for qualitative and quantitative assessment of MNZ pollutants, demonstrated by the integration of electrochemistry and spectroscopy and the critical role that 2D CoTe2-based sensors can play in accurate and efficient pesticide detection, which is required for agricultural safety protocols and environmental monitoring.},

note = {PMID: 39007738},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{doi:10.1021/acsaenm.4c00321,

title = {Subpicomolar Dopamine Detection Using Two-Dimensional Cobalt Telluride},

author = {Anyesha Chakraborty and Bruno Ipaves and Caique Campos de Oliveira and Solomon Demiss Negedu and Suman Sarkar and Basudev Lahiri and Pedro A. S. Autreto and Chandra Sekhar Tiwary},

url = {https://doi.org/10.1021/acsaenm.4c00321},

doi = {10.1021/acsaenm.4c00321},

year  = {2024},

date = {2024-07-11},

journal = {ACS Applied Engineering Materials},

volume = {0},

number = {0},

pages = {null},

abstract = {To address the challenges associated with ultrasensitive dopamine sensing for regular health monitoring, here we developed a flexible sensor using two-dimensional cobalt telluride (2D CoTe2). The 2D-CoTe2-coated glassy carbon electrode sensor shows a limit of detection (LoD) of 0.21 pM measured by differential pulse voltammetry (DPV) in 0.1 M phosphate buffer solution (PBS). The assessment of selectivity, repeatability, and reproducibility has been conducted, to enquire about the efficiency of the sensor. The durability of the sensor has been verified for a duration of one month, demonstrating a minimal loss of 16% after a period of one month. The interaction of the 2D CoTe2 and dopamine has been investigated thoroughly by chemical fingerprints using Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and Raman imaging, and the adsorption of dopamine on 2D CoTe2 has been confirmed by the theoretical calculations calculating the binding energy, differential charge densities, and projected density of states (pDOS). Additionally, a flexible paper-based sensor using 2D CoTe2 has been successfully fabricated and employed for real-time dopamine detection from artificial sweat, which achieved a LoD of 0.22 pM.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Sengupta2024,

title = {Deciphering Sodium‐Ion Storage: 2D‐Sulfide versus Oxide Through Experimental and Computational Analyses},

author = {Shilpi Sengupta and Atin Pramanik and Caique Campos de Oliveira and Shreyasi Chattopadhyay and Tymofii Pieshkov and Pedro A. S. Autreto and Pulickel M. Ajayan and Manab Kundu},

doi = {10.1002/smll.202403321},

issn = {1613-6829},

year  = {2024},

date = {2024-06-05},

urldate = {2024-06-05},

journal = {Small},

publisher = {Wiley},

abstract = {AbstractTransition metal derivatives exhibit high theoretical capacity, making them promising anode materials for sodium‐ion batteries. Sulfides, known for their superior electrical conductivity compared to oxides, enhance charge transfer, leading to improved electrochemical performance. Here, a hierarchical WS2 micro‐flower is synthesized by thermal sulfurization of WO3. Comprising interconnected thin nanosheets, this structure offers increased surface area, facilitating extensive internal surfaces for electrochemical redox reactions. The WS2 micro‐flower demonstrates a specific capacity of ≈334 mAh g−1 at 15 mA g−1, nearly three times higher than its oxide counterpart. Further, it shows very stable performance as a high‐temperature (65 °C) anode with ≈180 mAh g−1 reversible capacity at 100 mA g−1 current rate. Post‐cycling analysis confirms unchanged morphology, highlighting the structural stability and robustness of WS2. DFT calculations show that the electronic bandgap in both WS2 and WO3 increases when going from the bulk to monolayers. Na adsorption calculations show that Na atoms bind strongly in WO3 with a higher energy diffusion barrier when compared to WS2, corroborating the experimental findings. This study presents a significant insight into electrode material selection for sodium‐ion storage applications.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Khatun2024,

title = {Solid State Reaction Epitaxy, A New Approach for Synthesizing Van der Waals heterolayers: The Case of Mn and Cr on Bi_{2}Se_{3}},

author = {Salma Khatun and Onyedikachi Alanwoko and Vimukthi Pathirage and Caique C. de Oliveira and Raphael M. Tromer and Pedro A. S. Autreto and Douglas S. Galvao and Matthias Batzill},

doi = {10.1002/adfm.202315112},

issn = {1616-3028},

year  = {2024},

date = {2024-03-12},

urldate = {2024-03-12},

journal = {Adv Funct Materials},

publisher = {Wiley},

abstract = {AbstractVan der Waals (vdW) heterostructures that pair materials with diverse properties enable various quantum phenomena. However, the direct growth of vdW heterostructures is challenging. Modification of the surface layer of quantum materials to introduce new properties is an alternative process akin to solid state reaction. Here, vapor deposited transition metals (TMs), Cr and Mn, are reacted with Bi2Se3 with the goal to transform the surface layer to XBi2Se4 (X = Cr, Mn). Experiments and ab initio MD simulations demonstrate that the TMs have a high selenium affinity driving Se diffusion toward the TM. For monolayer Cr, the surface Bi2Se3 is reduced to Bi2‐layer and a stable (pseudo) 2D Cr1+δSe2 layer is formed. In contrast, monolayer Mn can transform upon mild annealing into MnBi2Se4. This phase only forms for a precise amount of initial Mn deposition. Sub‐monolayer amounts dissolve into the bulk, and multilayers form stable MnSe adlayers. This study highlights the delicate energy balance between adlayers and desired surface modified layers that governs the interface reactions and that the formation of stable adlayers can prevent the reaction with the substrate. The success of obtaining MnBi2Se4 points toward an approach for the engineering of other multicomponent vdW materials by surface reactions.},

keywords = {Biomaterials, Condensed Matter Physics, Electrochemistry, Electronic, Optical and Magnetic Materials},

pubstate = {published},

tppubtype = {article}

}

@article{LUCCHETTI2024108461,

title = {Cerium doped graphene-based materials towards oxygen reduction reaction catalysis},

author = {Lanna E. B. Lucchetti and Pedro A. S. Autreto and Mauro C. Santos and James M. de Almeida},

url = {https://www.sciencedirect.com/science/article/pii/S2352492824004410},

doi = {https://doi.org/10.1016/j.mtcomm.2024.108461},

issn = {2352-4928},

year  = {2024},

date = {2024-02-26},

urldate = {2024-02-26},

journal = {Materials Today Communications},

volume = {38},

pages = {108461},

abstract = {With the global transition towards cleaner energy and sustainable processes, the demand for efficient catalysts, especially for the oxygen reduction reaction, has gained attention from the scientific community. This research work investigates cerium-doped graphene-based materials as catalysts for this process with density functional theory calculations. The electrochemical performance of Ce-doped graphene was assessed within the computation hydrogen electrode framework. Our findings reveal that Ce doping, especially when synergized with an oxygen atom, shows improved catalytic activity and selectivity. For instance, Ce doping in combination with an oxygen atom, located near a border, can be selective for the 2-electron pathway. Overall, the combination of Ce doping with structural defects and oxygenated functions lowers the reaction free energies for the oxygen reduction compared to pure graphene, and consequently, might improve the catalytic activity. This research sheds light from a computational perspective on Ce-doped carbon materials as a sustainable alternative to traditional costly metal-based catalysts, offering promising prospects for green energy technologies and electrochemical applications.},

keywords = {Cerium, Density functional theory, Graphene, Oxygen reduction reaction},

pubstate = {published},

tppubtype = {article}

}

@article{TRENCH2024141456,

title = {Hydrogen peroxide electrogeneration from O2 electroreduction: A review focusing on carbon electrocatalysts and environmental applications},

author = {Aline B. Trench and Caio Machado Fernandes and João Paulo C. Moura and Lanna E. B. Lucchetti and Thays S. Lima and Vanessa S. Antonin and James M. de Almeida and 	Pedro A. S. Autreto and Irma Robles and Artur J. Motheo and Marcos R. V. Lanza and Mauro C. Santos},

url = {https://www.sciencedirect.com/science/article/pii/S0045653524003497},

doi = {https://doi.org/10.1016/j.chemosphere.2024.141456},

issn = {0045-6535},

year  = {2024},

date = {2024-02-15},

urldate = {2024-01-01},

journal = {Chemosphere},

pages = {141456},

abstract = {Hydrogen peroxide (H2O2) stands as one of the foremost utilized oxidizing agents in modern times. The established method for its production involves the intricate and costly anthraquinone process. However, a promising alternative pathway is the electrochemical hydrogen peroxide production, accomplished through the oxygen reduction reaction via a 2-electron pathway. This method not only simplifies the production process but also upholds environmental sustainability, especially when compared to the conventional anthraquinone method. In this review paper, recent works from the literature focusing on the 2-electron oxygen reduction reaction promoted by carbon electrocatalysts are summarized. The practical applications of these materials in the treatment of effluents contaminated with different pollutants (drugs, dyes, pesticides, and herbicides) are presented. Water treatment aiming to address these issues can be achieved through advanced oxidation electrochemical processes such as electro-Fenton, solar-electro-Fenton, and photo-electro-Fenton. These processes are discussed in detail in this work and the possible radicals that degrade the pollutants in each case are highlighted. The review broadens its scope to encompass contemporary computational simulations focused on the 2-electron oxygen reduction reaction, employing different models to describe carbon-based electrocatalysts. Finally, perspectives and future challenges in the area of carbon-based electrocatalysts for H2O2 electrogeneration are discussed. This review paper presents a forward-oriented viewpoint of present innovations and pragmatic implementations, delineating forthcoming challenges and prospects of this ever-evolving field.},

keywords = {Carbon materials, Environmental applications, Hydrogen peroxide, Oxygen reduction reaction, Theoretical simulations},

pubstate = {published},

tppubtype = {article}

}

@article{Mahapatra2023,

title = {Paramagnetic two-dimensional silicon-oxide from natural silicates},

author = {Preeti Lata Mahapatra and Caique Campos de Oliveira and Gelu Costin and Suman Sarkar and Pedro A. S. Autreto and Chandra Sekhar Tiwary},

url = {https://iopscience.iop.org/article/10.1088/2053-1583/ad10b9/meta},

doi = {10.1088/2053-1583/ad10b9},

issn = {2053-1583},

year  = {2023},

date = {2023-12-12},

urldate = {2024-01-01},

journal = {2D Mater.},

volume = {11},

number = {1},

publisher = {IOP Publishing},

abstract = {Abstract

               Silicon dioxide’s potential for having magnetic properties is fascinating, as combining its electronic capabilities with magnetic response seems promising for spintronics. In this work, the mechanisms that drive the change from diamagnetic behavior in pure silicates like SiO2 to paramagnetic behavior in transition metal-doped silicates like Rhodonite silicate (CaMn3Mn(Si5O15)) are explored. This naturally occurring Rhodonite (R)-silicate was thinned down while retaining its magnetic properties by liquid-phase scalable exfoliation. Exfoliating R-silicate into the two-dimensional (2D) structure by LPE increases magnetic coercivity, and the internal resistance to demagnetization (ΔHc) up to ∼23.95 Oe compared to 7.08 Oe for its bulk phase. DFT spin-polarized calculations corroborate those findings and explain that the origin of the magnetic moment comes mainly from the Mn in the doped 2D silicate due to the asymmetrical components of the Mn d and Si p states in the valence band. This result is further illustrated by the spin component differential charge densities showing that Mn and Si atoms display a residual up spin charge. Rhodonite’s unusual magnetic behavior has considerable potential for spintronics, data storage, and sensing technologies. Understanding the complex relationships between the structural, magnetic, and electronic properties of silicates is essential for developing new materials and composites as well as for driving future research.},

keywords = {Condensed Matter Physics, General Chemistry, General Materials Science, Mechanical Engineering, Mechanics of Materials},

pubstate = {published},

tppubtype = {article}

}

@article{MOURA2024112558,

title = {Ballistic properties of highly stretchable graphene kirigami pyramid},

author = {Alirio Moura and Bruno Ipaves and Douglas S. Galvao and Pedro A. S. Autreto},

url = {https://www.sciencedirect.com/science/article/pii/S0927025623005529},

doi = {https://doi.org/10.1016/j.commatsci.2023.112558},

issn = {0927-0256},

year  = {2023},

date = {2023-11-30},

urldate = {2024-01-01},

journal = {Computational Materials Science},

volume = {232},

pages = {112558},

abstract = {Graphene kirigamis, characterized by patterned cuts, can enhance some of the graphene’s mechanical and electronic properties. In this work, we report the first study of the mechanical and ballistic behavior of single and multi- layered graphene kirigami pyramid (GKP). We have carried out fully atomistic reactive molecular dynamics simulations. The GKP structures exhibit a large kinetic energy absorption capability due to their topology, which creates multi-step dissipation mechanisms that block crack propagation. Our results demonstrate that even having significantly less mass, GKP can outperform graphene structures of similar dimensions in terms of absorbing kinetic energy capabilities.},

keywords = {Ballistic properties, Kirigami, Molecular dynamics, reaxFF},

pubstate = {published},

tppubtype = {article}

}

@article{DeSousa2023,

title = {Boron nitride nanotube peapods at ultrasonic velocity impacts: a fully atomistic molecular dynamics investigation},

author = {J M De Sousa and L D Machado and C F Woellner and M Medina and Pedro A. S. Autreto and D S Galvão},

doi = {10.1088/1361-648x/acd50b},

issn = {1361-648X},

year  = {2023},

date = {2023-08-23},

urldate = {2023-08-23},

journal = {J. Phys.: Condens. Matter},

volume = {35},

number = {33},

publisher = {IOP Publishing},

abstract = {Abstract

               Boron nitride nanotube peapods (BNNT-peapod) are composed of linear chains of C60 molecules encapsulated inside BNNTs, they were first synthesized in 2003. In this work, we investigated the mechanical response and fracture dynamics of BNNT-peapods under ultrasonic velocity impacts (from 1 km s−1 up to 6 km s−1) against a solid target. We carried out fully atomistic reactive molecular dynamics simulations using a reactive force field. We have considered the case of horizontal and vertical shootings. Depending on the velocity values, we observed tube bending, tube fracture, and C60 ejection. Furthermore, the nanotube unzips for horizontal impacts at certain speeds, forming bi-layer nanoribbons ‘incrusted’ with C60 molecules. The methodology used here is applicable to other nanostructures. We hope it motivates other theoretical investigations on the behavior of nanostructures at ultrasonic velocity impacts and aid in interpreting future experimental results. It should be stressed that similar experiments and simulations were carried out on carbon nanotubes trying to obtain nanodiamonds. The present study expands these investigations to include BNNT.},

keywords = {Condensed Matter Physics, General Materials Science},

pubstate = {published},

tppubtype = {article}

}

@article{Antonin2023,

title = {Sodium niobate microcubes decorated with ceria nanorods for hydrogen peroxide electrogeneration: An experimental and theoretical study},

author = {Vanessa S. Antonin and Lanna E.B. Lucchetti and Felipe M. Souza and Victor S. Pinheiro and João P.C. Moura and Aline B. Trench and James M. de Almeida and Pedro A. S. Autreto and Marcos R.V. Lanza and Mauro C. Santos},

url = {https://www.sciencedirect.com/science/article/abs/pii/S092583882302666X},

doi = {10.1016/j.jallcom.2023.171363},

issn = {0925-8388},

year  = {2023},

date = {2023-07-21},

urldate = {2023-11-00},

journal = {Journal of Alloys and Compounds},

volume = {965},

publisher = {Elsevier BV},

abstract = {The present work investigates the catalytic activity of NaNbO3 microcubes decorated with CeO2 nanorods on carbon (1 %, 3 %, 5 %, and 10 % w/w) for H2O2 electrogeneration. The crystalline phases and the morphology of the materials were identified with scanning electron microscopy, transmission electron microscopy, X‐ray diffraction and X-ray Photoelectronic spectroscopy. Contact angle measurements were performed to characterize the hydrophilicity of each material. The H2O2 electrogeneration was assessed by oxygen reduction reaction using the rotating ring-disk electrode technique. Electrochemical characterization results shown an enhancement on the H2O2 electrogeneration by NaNbO3 @CeO2/C-based materials compared to what was obtained with pure Vulcan XC72. The 1 % NaNbO3 @CeO2/C electrocatalyst presented the lower starting potential for the ORR and a 2.3 electron transfer, favoring the 2-electron mechanism and providing a higher H2O2 electrogeneration rate. Also, the enhancement of oxygen-containing functional groups showed the potential to comprehensively tune properties and optimize active sites and, consequently, increases the H2O2 electrogeneration. Density functional theory calculations indicated that NaNbO3 and CeO2 surfaces have a similar low theoretical overpotential for this reaction and that CeO2 improves the catalyst facilitating the electron transfer. These results indicate that NaNbO3 @CeO2/C-based electrocatalysts are promising materials for in situ H2O2 electrogeneration.},

keywords = {Materials Chemistry, Mechanical Engineering, Mechanics of Materials, Metals and Alloys},

pubstate = {published},

tppubtype = {article}

}

@article{Oliveira2023b,

title = {Optimized 2D nanostructures for catalysis of hydrogen evolution reactions},

author = {Caique Campos de Oliveira and Pedro A. S. Autreto},

doi = {10.1557/s43580-023-00549-7},

issn = {2059-8521},

year  = {2023},

date = {2023-06-00},

urldate = {2023-06-00},

journal = {MRS Advances},

volume = {8},

number = {6},

pages = {307--310},

publisher = {Springer Science and Business Media LLC},

keywords = {Condensed Matter Physics, General Materials Science, Mechanical Engineering, Mechanics of Materials},

pubstate = {published},

tppubtype = {article}

}

@article{Lucchetti2023,

title = {Unravelling catalytic activity trends in ceria surfaces toward the oxygen reduction and water oxidation reactions},

author = {Lanna E. B. Lucchetti and Pedro A. S. Autreto and James M. de Almeida and Mauro C. Santos and Samira Siahrostami},

doi = {10.1039/d3re00027c},

issn = {2058-9883},

year  = {2023},

date = {2023-05-30},

journal = {React. Chem. Eng.},

volume = {8},

number = {6},

pages = {1285--1293},

publisher = {Royal Society of Chemistry (RSC)},

abstract = {Different facets of ceria exhibit activities for the entire spectrum of oxygen electrochemistry.},

keywords = {Catalysis, Chemical Engineering (miscellaneous), Chemistry (miscellaneous), Fluid Flow and Transfer Processes, Process Chemistry and Technology},

pubstate = {published},

tppubtype = {article}

}

@article{Oliveira2023,

title = {Tetra-penta-deca-hexagonal-graphene (TPDH-graphene) hydrogenation patterns: dynamics and electronic structure},

author = {Caique C. Oliveira and Matheus Medina and Douglas S. Galvao and Pedro A. S. Autreto},

doi = {10.1039/d3cp00186e},

issn = {1463-9084},

year  = {2023},

date = {2023-05-10},

journal = {Phys. Chem. Chem. Phys.},

volume = {25},

number = {18},

pages = {13088--13093},

publisher = {Royal Society of Chemistry (RSC)},

abstract = {Fully atomistic molecular dynamics and density functional theory of hydrogenation process on 2D carbon allotrope: tetra-penta-deca-hexagonal graphene.},

keywords = {General Physics and Astronomy, Physical and Theoretical Chemistry},

pubstate = {published},

tppubtype = {article}

}